CN107722258A - A kind of continuous producing method of bio-based polymers PPG - Google Patents
A kind of continuous producing method of bio-based polymers PPG Download PDFInfo
- Publication number
- CN107722258A CN107722258A CN201710915808.6A CN201710915808A CN107722258A CN 107722258 A CN107722258 A CN 107722258A CN 201710915808 A CN201710915808 A CN 201710915808A CN 107722258 A CN107722258 A CN 107722258A
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- CN
- China
- Prior art keywords
- polyethers
- polyether polyol
- producing method
- continuous producing
- vegetable oil
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
Abstract
The present invention relates to a kind of continuous producing method of biobased polyether polyol, this method uses the oily Ester of bio-based as initiator, the continuous polymerization expoxy propane under potassium hydroxide or bimetallic catalytic, aggregate into PPG, after polyethers synthesis, polyethers based on this PPG is reused, polyether polyol is produced using continuous production mode.The method of the present invention is greatly reduced can regenerate for petroleum-based dependence, raw material.And due to there is partial double bond in basic polyether, partial double bond polymerize with styrene-acrylonitrile, good dispersion stabilizer effect is played, caused bulky grain in course of reaction is effectively reduced, improves the stability of polyether polyol.
Description
Technical field
The present invention relates to a kind of continuous producing method of bio-based polymers PPG, belong to the system of PPG
Standby technical field.
Background technology
With the development of polyurethane industries among others, polyurethane production grows steadily with consumption figure, and polyurethane industries among others are for epoxy third
The consumption figure of alkane is also steady growth, and expoxy propane derives from petrochemical industry, with progressively in short supply, the price of petroleum resources
And skyrocket.And the resource of bio-based increasingly obtains our attention due to its recyclability.The polyalcohol application mesh of bio-based
It is preceding domestic also relatively more.
The polyalcohol of current domestic bio-based is all concentrated use in hard bubble field, and biopolyol is in hard bubble field
Also part steady production has been formed.And in polyether polyol for soft PU foam field using less, soft bubble polyethers is made with glycerine at present
For initiator, expoxy propane and oxirane are as chain extender, and the petroleum derivative of the inside more than 98%, petroleum resources are can not
Regenerated resources, as expanding economy drains off.Chinese patent CN102532513 uses vegetable oil synthesis certain molecular weight
Soft bubble polyethers.
The content of the invention：
In view of the shortcomings of the prior art, the present invention provides a kind of continuous producing method of bio-based polymers PPG, this
Invention under bimetallic catalyst or KOH catalysis, polymerize expoxy propane, obtains PPG using vegetable oil as initiator
, this method reduces the dependence to oil using vegetable oil as raw material, and obtained biobased polyether polyol has good stable dispersion
Effect, makes polymerized monomer be stably dispersed in system, avoids the generation of aggregated particles.
The present invention is achieved through the following technical solutions：
A kind of continuous producing method of bio-based polymers PPG, including；
Hydroxyl value is 56 polyethers A preparation processes；
Hydroxyl value is 56 polyethers B preparation processes；
Polyethers based on polyethers A or polyethers B, bio-based polymers polyether polyols are made by polymerisation with polymerized monomer
Alcohol.
It is that 56 polyethers A preparation processes are according to currently preferred, described hydroxyl value：Vegetable oil presses quality with potassium hydroxide
100:It is dehydrated after 0.2-0.3 mixing, is passed through expoxy propane（PO）, aging to negative pressure, then add water, in phosphoric acid and PH=5-7,
Add adsorbent and dehydration is dried, it is 56 polyethers A to obtain hydroxyl value.
It is further preferred that dehydration is after described vegetable oil mixes with potassium hydroxide：Mixture is dry in 120-130 DEG C
Dry 2-4 hours, it is less than 0.05% to water content.
It is further preferred that expoxy propane（PO）The environment that is passed through be 120-130 DEG C of temperature, insulation reacted, epoxy
Propane（PO）Addition account for the 60-70% of vegetable oil and potassium hydroxide amount of the mixture.
It is further preferred that the addition of water accounts for the 1-5% of vegetable oil and potassium hydroxide amount of the mixture, the addition of phosphoric acid
Amount accounts for the 0.5-0.6% of vegetable oil and potassium hydroxide amount of the mixture.
It is further preferred that being warming up to 120-130 DEG C of dry 2-4 hour after adding adsorbent, it is less than to water content
0.05%, it is 56 polyethers A to obtain hydroxyl value.
It is that 56 polyethers B preparation processes are according to currently preferred, described hydroxyl value：Vegetable oil is pressed with bimetallic catalyst
Quality 1000:It is dehydrated after 0.02-0.05 mixing, is passed through expoxy propane（PO）, it is 56 polyethers B to react obtained hydroxyl value.
It is further preferred that dehydration is after described sesame oil mixes with bimetallic catalyst：By mixture in 120-130 DEG C
2-4 hours are dried, are less than 0.05% to water content.
It is further preferred that expoxy propane（PO）The environment that is passed through be 130 DEG C of temperature, insulation reacted, expoxy propane
（PO）Addition account for the 50%-60% of vegetable oil and bimetallic catalyst amount of the mixture.
It is hydroxylating soybean oil or castor oil according to currently preferred, described vegetable oil.
According to currently preferred, polyethers A or polyethers B and polymer monomer with（50-55）：（40-50）Mixing, addition are drawn
Agent is sent out, polymerisation is carried out under the conditions of 100 DEG C -130 DEG C of temperature, pressure 0.5MP, obtains bio-based polymers polyether polyols
Alcohol.
According to currently preferred, the addition of initiator accounts for polyethers A or polyethers B and polymer monomer total amount 2-4%.
It is styrene and acrylonitrile monemer according to currently preferred, described polymer monomer, ethene, acrylonitrile monemer
Mass ratio accounts for the 20%-50% of whole system altogether,
It is azodiisobutyronitrile according to currently preferred, described initiator.
The effect of the present invention：
The present invention uses the oily Ester of bio-based as initiator, the continuous polymerization under potassium hydroxide or bimetallic catalytic
Expoxy propane, aggregate into the PPG of certain molecular weight, if the polyethers that potassium hydroxide synthesizes as catalyst, it is necessary to
Post processing removes potassium hydroxide, obtains pure polyethers.If the polyethers of bimetallic catalyst synthesis need not then post-process.
After polyethers synthesis, polyethers based on this PPG is reused, it is more to produce polyether using continuous production mode
First alcohol.Synthesizing high-stability polyether polyol, the mode of production of this polyether polyol can be greatly reduced
For petroleum-based dependence, raw material can regenerate.And due to having partial double bond, partial double bond and styrene third in basic polyether
Alkene nitrile polymerize, and plays good dispersion stabilizer effect, effectively reduces caused bulky grain in course of reaction, improve polymerization
The stability of thing PPG.
Embodiment
With reference to specific embodiment, the present invention is described further, but not limited to this.
Experimental method described in following embodiments simultaneously, is conventional method unless otherwise specified；The material, such as nothing
Specified otherwise, commercially obtain.
Embodiment 1
A kind of continuous producing method of bio-based polymers PPG, step are as follows：
（1）, vegetable oil 350g added in kettle, add 2g KOH, 120-130 DEG C of vacuum dehydration 2 hours, 120-130 DEG C is logical
Enter 750g expoxy propane, led to aging to negative pressure, added 30g pure water, add in 4g phosphoric acid and PH=5-7, addition adsorbent heat up
It is dehydrated 2 hours to 120-130 DEG C, is less than 0.05% to moisture, filters to obtain polyethers A；
（2）, by polyethers A and polymer monomer with 55：44 mix, and add 2% new initiator, macromolcular dispersant, trigger
Agent, continuously added after well mixed in reactor, the temperature of reactor is kept for 100 DEG C -130 DEG C, and pressure is entered in 0.5MP
Row polymerisation, material continuously enter vacuum system by the overfall on reactor top, and vacuum system removing is unreacted
Monomer and initiator, so as to obtain qualified polyether polyol C.
Embodiment 2
A kind of continuous producing method of bio-based polymers PPG, step are as follows：
（1）Vegetable oil 350g is added in kettle, adds 0.05g bimetallic catalyst, 120-130 DEG C of vacuum dehydration 2 hours,
120-130 DEG C is passed through 750g expoxy propane, has led to aging to negative pressure, cooling discharge obtains polyethers B
（2）By polyethers B and polymer monomer with 50：50 mix, and add 2% new initiator, macromolcular dispersant, trigger
Agent, continuously added after well mixed in reactor, the temperature of reactor is kept for 100 DEG C -130 DEG C, and pressure is entered in 0.5MP
Row polymerisation, material continuously enter vacuum system by the overfall on reactor top, and vacuum system removing is unreacted
Monomer and initiator, so as to obtain qualified polyether polyol D.
Experimental example：
Flexible polyurethane foams are made in the bio-based polymers PPG of the present invention, and performance detection and stability result are such as
Shown in table 1 below, table 2.
The product formula of table 1 and performance detection
The product formula of table 2 and stability
| Project | Stability |
| 2045 | 1 year |
| Polymer polyatomic alcohol C | 2 years |
| Polymer polyatomic alcohol D | 2 years |
Claims (10)
1. a kind of continuous producing method of biobased polyether polyol, including；
Hydroxyl value is 56 polyethers A preparation processes；
Hydroxyl value is 56 polyethers B preparation processes；
Polyethers based on polyethers A or polyethers B, biobased polyether polyol is made by polymerisation with polymerized monomer.
2. the continuous producing method of biobased polyether polyol according to claim 1, it is characterised in that described hydroxyl value
It is for 56 polyethers A preparation processes：Vegetable oil presses quality 100 with potassium hydroxide:It is dehydrated after 0.2-0.3 mixing, is passed through expoxy propane
（PO）, aging to negative pressure, is then added in water, phosphoric acid and dehydration is dried in PH=5-7, addition adsorbent, obtains hydroxyl value as 56
Polyethers A.
3. the continuous producing method of biobased polyether polyol according to claim 2, it is characterised in that described plant
Oil is dehydrated after being mixed with potassium hydroxide：By mixture in 120-130 DEG C of dry 2-4 hour, it is less than 0.05% to water content.
4. the continuous producing method of biobased polyether polyol according to claim 2, it is characterised in that expoxy propane
（PO）The environment that is passed through be 120-130 DEG C of temperature, insulation reacted, expoxy propane（PO）Addition account for vegetable oil and hydrogen-oxygen
Change the 60-70% of potassium amount of the mixture, the addition of water accounts for the 1-5% of vegetable oil and potassium hydroxide amount of the mixture, and phosphoric acid adds
Enter the 0.5-0.6% that amount accounts for vegetable oil and potassium hydroxide amount of the mixture.
5. the continuous producing method of biobased polyether polyol according to claim 2, it is characterised in that add adsorbent
After be warming up to 120-130 DEG C of dry 2-4 hour, to water content be less than 0.05%, it is 56 polyethers A to obtain hydroxyl value.
6. the continuous producing method of biobased polyether polyol according to claim 1, it is characterised in that described hydroxyl value
It is for 56 polyethers B preparation processes：Vegetable oil presses quality 1000 with bimetallic catalyst:It is dehydrated after 0.02-0.05 mixing, is passed through ring
Ethylene Oxide（PO）, it is 56 polyethers B to react obtained hydroxyl value.
7. the continuous producing method of biobased polyether polyol according to claim 6, it is characterised in that described sesame oil
It is dehydrated after being mixed with bimetallic catalyst and is：By mixture in 120-130 DEG C of dry 2-4 hour, it is less than 0.05% to water content；
Expoxy propane（PO）The environment that is passed through be 130 DEG C of temperature, insulation reacted, expoxy propane（PO）Addition account for vegetable oil with
The 50%-60% of bimetallic catalyst amount of the mixture.
8. the continuous producing method of the biobased polyether polyol according to claim 2 or 6, it is characterised in that described
Vegetable oil is hydroxylating soybean oil or castor oil.
9. the continuous producing method of biobased polyether polyol according to claim 1, it is characterised in that polyethers A or poly-
Ether B and polymer monomer with（50-55）：（40-50）Mixing, initiator is added, in 100 DEG C -130 DEG C of temperature, pressure 0.5MP bars
Polymerisation is carried out under part, obtains biobased polyether polyol.
10. the continuous producing method of biobased polyether polyol according to claim 9, it is characterised in that initiator
Addition accounts for polyethers A or polyethers B and polymer monomer total amount 2-4%, and described polymer monomer is styrene and acrylonitrile list
Body, ethene, acrylonitrile monemer mass ratio account for the 20%-50% of whole system altogether, and described initiator is azodiisobutyronitrile.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710915808.6A CN107722258A (en) | 2017-09-30 | 2017-09-30 | A kind of continuous producing method of bio-based polymers PPG |
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| CN201710915808.6A CN107722258A (en) | 2017-09-30 | 2017-09-30 | A kind of continuous producing method of bio-based polymers PPG |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003418A (en) * | 2019-04-24 | 2019-07-12 | 东莞市腾崴塑胶制品有限公司 | A kind of biopolyol sponge and preparation method |
| CN113980205A (en) * | 2021-12-06 | 2022-01-28 | 山东蓝星东大有限公司 | Process for preparing polymer polyols |
| CN113980205B (en) * | 2021-12-06 | 2024-05-03 | 中化东大(淄博)有限公司 | Process for preparing polymer polyols |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312302A (en) * | 2001-02-27 | 2001-09-12 | 青岛化工学院 | Continuous prepn of polyether polyol |
| CN101218272A (en) * | 2005-03-03 | 2008-07-09 | 南达科他大豆处理机有限公司 | Novel polyols derived from a vegetable oil using an oxidation process |
| CN101792512A (en) * | 2008-12-23 | 2010-08-04 | 拜尔材料科学有限公司 | Polymer polyols comprising a natural oil base polyol, polyurethane foams comprising these polymer polyols and processes for their preparation |
| CN102167809A (en) * | 2011-03-08 | 2011-08-31 | 江苏绿源新材料有限公司 | Method for preparing biobased polyether polylol from vegetable oil |
| CN102603997A (en) * | 2012-02-29 | 2012-07-25 | 南京金浦锦湖化工有限公司 | Continuous method for producing polymer polyether polyol |
| CN104540876A (en) * | 2012-07-20 | 2015-04-22 | 拜尔材料科学有限公司 | A process for the in situ production of polyether polyols based on renewable materials and their use in the production of flexible polyurethane foams |
-
2017
- 2017-09-30 CN CN201710915808.6A patent/CN107722258A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312302A (en) * | 2001-02-27 | 2001-09-12 | 青岛化工学院 | Continuous prepn of polyether polyol |
| CN101218272A (en) * | 2005-03-03 | 2008-07-09 | 南达科他大豆处理机有限公司 | Novel polyols derived from a vegetable oil using an oxidation process |
| CN101792512A (en) * | 2008-12-23 | 2010-08-04 | 拜尔材料科学有限公司 | Polymer polyols comprising a natural oil base polyol, polyurethane foams comprising these polymer polyols and processes for their preparation |
| CN102167809A (en) * | 2011-03-08 | 2011-08-31 | 江苏绿源新材料有限公司 | Method for preparing biobased polyether polylol from vegetable oil |
| CN102603997A (en) * | 2012-02-29 | 2012-07-25 | 南京金浦锦湖化工有限公司 | Continuous method for producing polymer polyether polyol |
| CN104540876A (en) * | 2012-07-20 | 2015-04-22 | 拜尔材料科学有限公司 | A process for the in situ production of polyether polyols based on renewable materials and their use in the production of flexible polyurethane foams |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003418A (en) * | 2019-04-24 | 2019-07-12 | 东莞市腾崴塑胶制品有限公司 | A kind of biopolyol sponge and preparation method |
| CN113980205A (en) * | 2021-12-06 | 2022-01-28 | 山东蓝星东大有限公司 | Process for preparing polymer polyols |
| CN113980205B (en) * | 2021-12-06 | 2024-05-03 | 中化东大(淄博)有限公司 | Process for preparing polymer polyols |
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